Ab Initio Molecular Dynamics Insight to Structural Phase Transition and Thermal Decomposition of InN.

Extensive ab initio density functional theory molecular dynamics calculations were used to evaluate stability conditions for relevant phases of InN. In particular, the p-T conditions of the thermal decomposition of InN and pressure-induced wurtzite-rocksalt solid-solid phase transition were established. The comparison of the simulation results with the available experimental data allowed for a critical evaluation of the capabilities and limitations of the proposed simulation method. It is shown that ab initio molecular dynamics can be used as an efficient tool for simulations of phase transformations of InN, including solid-solid structural transition and thermal decomposition with formation of N2 molecules. It is of high interest, because InN is an important component of epitaxial quantum structures, but it has not been obtained as a bulk single crystal. This makes it difficult to determine its basic physical properties to develop new applications.

Intercalating Architecture for the Design of Charge Density Wave in Metallic MA2Z4 Materials.

We present a novel approach to induce charge density waves (CDWs) in metallic MA2Z4 materials, resembling the behavior observed in transition metal dichalcogenides (TMDCs). This method leverages the intercalating architecture to maintain the same crystal field and Fermi surface topologies. Our investigation reveals that CDW instability in these materials arises from electron-phonon coupling (EPC) between the d band and longitudinal acoustic (LA) phonons, mirroring TMDC's behavior. By combining α-MA2Z4 with 1H-MX2 materials in a predictive CDW phase diagram using critical EPC constants, we demonstrate the feasibility of extending CDW across material families with comparable crystal fields and reveal the crucial role in CDW instability of the competition between ionic charge transfer and electron correlation. We further uncover a strain-induced Mott transition in ß2-NbGe2N4 monolayer featuring star-of-David patterns. This work highlights the potential of intercalating architecture to engineer CDW materials, expanding our understanding of CDW instability and correlation physics.

Enhanced Ferromagnetism and Tunable Magnetic Anisotropy in a van der Waals Ferromagnet.

2D van der Waals (vdW) magnets have recently emerged as a promising material system for spintronic device innovations due to their intriguing phenomena in the reduced dimension and simple integration of magnetic heterostructures without the restriction of lattice matching. However, it is still challenging to realize Curie temperature far above room temperature and controllable magnetic anisotropy for spintronics application in 2D vdW magnetic materials. In this work, the pressure-tuned dome-like ferromagnetic-paramagnetic phase diagram in an iron-based 2D layered ferromagnet Fe3GaTe2 is reported. Continuously tunable magnetic anisotropy from out-of-plane to in-plane direction is achieved via the application of pressure. Such behavior is attributed to the competition between intralayer and interlayer exchange interactions and enhanced DOS near the Fermi level. The study presents the prominent properties of pressure-engineered 2D ferromagnetic materials, which can be used in the next-generation spintronic devices.

Cuprate-like electronic structures in infinite-layer nickelates with substantial hole dopings.

Superconducting infinite-layer (IL) nickelates offer a new platform for investigating the long-standing problem of high-temperature superconductivity. Many models were proposed to understand the superconducting mechanism of nickelates based on the calculated electronic structure, and the multiple Fermi surfaces and multiple orbitals involved create complications and controversial conclusions. Over the past five years, the lack of direct measurements of the electronic structure has hindered the understanding of nickelate superconductors. Here we fill this gap by directly resolving the electronic structures of the parent compound LaNiO2 and superconducting La0.8Ca0.2NiO2 using angle-resolved photoemission spectroscopy. We find that their Fermi surfaces consist of a quasi-2D hole pocket and a 3D electron pocket at the Brillouin zone corner, whose volumes change upon Ca doping. The Fermi surface topology and band dispersion of the hole pocket closely resemble those observed in hole-doped cuprates. However, the cuprate-like band exhibits significantly higher hole doping in superconducting La0.8Ca0.2NiO2 compared to superconducting cuprates, highlighting the disparities in the electronic states of the superconducting phase. Our observations highlight the novel aspects of the IL nickelates, and pave the way toward the microscopic understanding of the IL nickelate family and its superconductivity.

Electrifying HCOOH synthesis from CO2 building blocks over Cu-Bi nanorod arrays.

Precise electrochemical synthesis of commodity chemicals and fuels from CO2 building blocks provides a promising route to close the anthropogenic carbon cycle, in which renewable but intermittent electricity could be stored within the greenhouse gas molecules. Here, we report state-of-the-art CO2-to-HCOOH valorization performance over a multiscale optimized Cu-Bi cathodic architecture, delivering a formate Faradaic efficiency exceeding 95% within an aqueous electrolyzer, a C-basis HCOOH purity above 99.8% within a solid-state electrolyzer operated at 100 mA cm-2 for 200 h and an energy efficiency of 39.2%, as well as a tunable aqueous HCOOH concentration ranging from 2.7 to 92.1 wt%. Via a combined two-dimensional reaction phase diagram and finite element analysis, we highlight the role of local geometries of Cu and Bi in branching the adsorption strength for key intermediates like *COOH and *OCHO for CO2 reduction, while the crystal orbital Hamiltonian population analysis rationalizes the vital contribution from moderate binding strength of η2(O,O)-OCHO on Cu-doped Bi surface in promoting HCOOH electrosynthesis. The findings of this study not only shed light on the tuning knobs for precise CO2 valorization, but also provide a different research paradigm for advancing the activity and selectivity optimization in a broad range of electrosynthetic systems.

Ductile P-Type AgCu(Se,S,Te) Thermoelectric Materials.

Ductile inorganic thermoelectric (TE) materials open a new approach to develop high-performance flexible TE devices. N-type Ag2(S,Se,Te) and p-type AgCu(Se,S,Te) pseudoternary solid solutions are two typical categories of ductile inorganic TE materials reported so far. Comparing with the Ag2(S,Se,Te) pseudoternary solid solutions, the phase composition, crystal structure, and physical properties of AgCu(Se,S,Te) pseudoternary solid solutions are more complex, but their relationships are still ambiguous now. In this work, via systematically investigating the phase composition, crystal structure, mechanical, and TE properties of about 60 AgCu(Se,S,Te) pseudoternary solid solutions, the comprehensive composition-structure-property phase diagrams of the AgCuSe-AgCuS-AgCuTe pseudoternary system is constructed. By mapping the complex phases, the "ductile-brittle" and "n-p" transition boundaries are determined and the composition ranges with high TE performance and inherent ductility are illustrated. On this basis, high performance p-type ductile TE materials are obtained, with a maximum zT of 0.81 at 340 K. Finally, flexible in-plane TE devices are prepared by using the AgCu(Se,S,Te)-based ductile TE materials, showing high output performance that is superior to those of organic and inorganic-organic hybrid flexible devices.

Self-Emulsifying Drug Delivery Systems: Concept to Applications, Regulatory Issues, Recent Patents, Current Challenges and Future Directions.

Self-emulsifying drug delivery systems (SEDDS) can increase the solubility and bioavailability of poorly soluble drugs. The inability of 35% to 40% of new pharmaceuticals to dissolve in water presents a serious challenge for the pharmaceutical industry. As a result, there must be dosage proportionality, considerable intra- and inter-subject variability, poor solubility, and limited lung bioavailability. As a result, it is critical that drugs intended for oral administration be highly soluble. This can be improved through a variety of means, including salt generation and the facilitation of solid and complicated dispersion. Surfactants, lubricants, and cosolvents may occasionally be found in SEDDS or isotropic blends. Lipophilic drugs, whose absorption is limited by their dissolution rate, have been used to demonstrate the effectiveness of various formulations and techniques. These particles can form microemulsions and suitable oil-inwater emulsions with minimal agitation and dilution by the water phase as they pass through the gastrointestinal tract. This study summarises the numerous advances, biopharmaceutical components, variations, production techniques, characterisation approaches, limitations, and opportunities for SEDDS. With this context in mind, this review compiles a current account of biopharmaceutical advancements, such as the application of quality by design (QbD) methodologies to optimise drug formulations in different excipients with controllable ratios, the presence of regulatory roadblocks to progress, and the future consequences of SEDDS, encompassing composition, evaluation, diverse dosage forms, and innovative techniques for in vitro converting liquid SEDDS to solid forms.

Natural tristability of a confined helical filament with anisotropic bending rigidities.

We find that when c 0 R ∼ 0.5 and τ 0 R < 0.11 < c 0 R , confining a helical filament with anisotropic bending rigidities within a cylindrical tube of radius R can create a natural tristable status which is consisted of two low-pitch helices and one high-pitch helix, where a helical filament is referred to as a filament that has both an intrinsic curvature ( c 0 ) and an intrinsic twist rate ( τ 0 ). The formation of the tristable status also requires that the filament has a significant difference between two bending rigidities and a large twisting rigidity. The relative heights of two low-pitch helices in a tristable status are close to zero, and the smaller the intrinsic twisting angle, the smaller the difference between these two heights. Moreover, at a large intrinsic twisting angle, two low-pitch helices display a large energy difference, and the energy difference increases with decreasing τ 0 . Meanwhile, the relative height of the high-pitch helix is always close to that of a straight line. Finally, at some specific intrinsic parameters, the tristable status can include an isoenergic status with two helices of the same energy but distinct pitches.

Molecular symmetry change of perfluoro-n-alkanes in 'Phase I' monitored by infrared spectroscopy.

Phase diagram of polytetrafluoroethylene (PTFE) comprises four regions. Phases II and IV are characterized by twisted perfluoroalkyl (Rf) chains having different twisting rate of 13/6 and 15/7, respectively, while Phase III is characterized by a planer trans-zigzag molecular skeleton like a normal alkyl chain. These are confirmed by X-ray and electron diffraction and have already been established. Unlike these, Phase I is left an unresolved matter. This phase is complicated indeed and is not symbolized by a single molecular structure. At an ambient pressure, Phase I is the temperature region above 30 ºC (303 K), and the helical molecular structure is supposed to be gradually untwisted with an elevating temperature. This untwisting image is roughly suggested by the diffraction, neutron scattering, and thermal expansion techniques, but the conventional approaches have all experimental limitations because the untwisting accompanies disorder (or defect) in the twist along the chain. To explore the transition between two different helical structures of the Rf chain having disordered structures, vibrational spectroscopic techniques are expected to be an alternative approach. For infrared spectroscopy, for example, the twisting rate of the molecule is simply recognized as a degree of molecular symmetry. Here, we show that the band progression peaks of the CF2 symmetric stretching vibration mode are quite sensitive and useful for pursuing the molecular symmetry change in Phase I for both peak intensity and position using perfluoro-n-alkanes having different chain length covering both even and odd number of the CF2 groups.

Probe into a novel surfactant-free microemulsion system of ethylene glycol monobutyl ether + water + diesel for crude oil removal and recovery from oily sludge.

A novel surfactant-free microemulsion (SFME) system was proposed in this study, and applied in the crude oil removal and recovery from oily sludge (OS). Based on an investigation of the SFME phase behavior and solution properties, a complete ternary phase diagram was constructed. The SFME with three-liquid phase equilibrium (Winsor III type) was selected for the treatment of OS to achieve simultaneous efficient removal (up to 95.1 %) and recovery (up to 83.2 %) of crude oil. The SFME could be reused continuously for OS treatment without purification. The removal efficiency could still keep >75.9 % after 5 times of reuse, showing high reusability. The detached crude oil could be automatically recovered based on the phase equilibrium principle without additional separation. In the washing experiments, single-factor and multi-factor orthogonal tests were applied to investigate the effects of different experimental conditions on oil removal efficiency and determine the optimal experimental scheme. The treated OS was sufficiently decontaminated according to the morphology, composition, and properties analysis by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and contact angle. The composition of the recovered crude oil was identical to that of commercial crude oil according to gas chromatography-mass spectrometry analysis, showing a high recovery value. The kinetic analysis revealed that crude oil desorption experienced three main stages: membrane diffusion, intra-particle diffusion and surface desorption, and identified the chemisorption was the main interaction between the oil-soil. Finally, the mechanism of SFME action was assessed for dissolution and activation based on ultra-low IFT.

A new order parameter model for the improper ferroelastic phase transitions in KMnF3 single crystal.

This paper proposes a new order parameter model which satisfactorily explains complicated symmetry changes, the temperature-pressure (T-P) phase diagram and elastic anomalies observed experimentally with the improper ferroelastic phase transitions in multiferroic KMnF3 single crystal. First, it is shown that the order parameter model is transformed according to the four-dimensional reducible representation of the wavevector star channel group. Second, based on the order parameter model and the singularity theory, the sixth-order structurally stable Landau potential model is constructed. Finally, the theoretical T-P phase diagram is plotted and the elastic anomalies possible for each of the phase transitions are discussed.

Disodium Cromoglycate Templates Anisotropic Short-Chain PEG Hydrogels.

Anisotropic hydrogels have found widespread applications in biomedical engineering, particularly as scaffolds for tissue engineering. However, it remains a challenge to produce them using conventional fabrication methods, without specialized synthesis or equipment, such as 3D printing and unidirectional stretching. In this study, we explore the self-assembly behaviors of polyethylene glycol diacrylate (PEGDA), using disodium cromoglycate (DSCG), a lyotropic chromonic liquid crystal, as a removable template. The affinity between short-chain PEGDA (Mn = 250) and DSCG allows polymerization to take place at the DSCG surface, thereby forming anisotropic hydrogel networks with fibrin-like morphologies. This process requires considerable finesse as the phase behaviors of DSCG depend on a multitude of factors, including the weight percentage of PEGDA and DSCG, the chain length of PEGDA, and the concentration of ionic species. The key to modulating the microstructures of the all-PEG hydrogel networks is through precise control of the DSCG concentration, resulting in anisotropic mechanical properties. Using these anisotropic hydrogel networks, we demonstrate that human dermal fibroblasts are particularly sensitive to the alignment order. We find that cells exhibit a density-dependent activation pattern of a Yes-associated protein, a mechanotransducer, corroborating its role in enabling cells to translate external mechanical and morphological patterns to specific behaviors. The flexibility of modulating microstructure, along with PEG hydrogels' biocompatibility and biodegradability, underscores their potential use for tissue engineering to create functional structures with physiological morphologies.

Biomimetic Capsid-Like Nanoshells Self-Assembled from Homopolypeptides.

The preparation of capsid-like nanoshells and the elucidation of their formation pathways are crucial for the application potential of capsid-like nanomaterials. In this study, we have prepared biomimetic capsid-like nanoshells (CLNs) through the solution self-assembly of poly (ß-phenethyl-L-aspartate) homopolypeptide (PPLA). The formation of CLNs is governed by an aggregation-fusion mechanism. Initially, PPLA molecules self-assemble into small spherical assemblies as subunits and the initial nuclei are formed through fusing some subunits. Subsequently, additional subunits rapidly fuse onto these nuclei, leading to the growth of full or partial CLNs during the growth phase. Moreover, the suitable condition benefiting CLNs formation is clarified by a morphological phase diagram based on the initial PPLA concentration against water content. Molecular-level measurements suggest that the molecular flexibility of PPLA is a key factor in the arrangement and fusion of subunits for the formation of CLNs. These findings offer new perspectives for a deeper understanding of the formation pathways of capsid-like nanoshells derived from synthetic polymers.

The Influence of Al and Nb on the Low Oxygen Pressure Pre-Oxidation Behavior of Fe-35Ni-20Cr-xAl-yNb Alloys at 1000 °C.

To investigate the impact of Al and Nb elements on the formation of a protective oxide layer on the surface of Fe-35Ni-20Cr-xAl-yNb (x = 0, 2, 4, 6 wt.%; y = 0, 1, 2 wt.%) alloys, their oxidation behavior was examined at 1000 °C, 10-17 atm. and 10-25 atm. oxygen pressure, and the oxidation mechanism was analyzed by Factsage and Pandat calculations. Enhancing the Al content at 10-17 atm. inhibited the generation of FeCr2O4 on the alloy surface and increased the Al content in the M2O3 layer. When the Al content exceeded 6 wt.%, the oxide film partially peeled off. It was found that the addition of Nb increased the activity of Cr and Al and decreased the activity of Ni and Fe and promoted the formation of Al2O3, and the appearance of Nb2O5 in the subsurface layer increased the density of the oxide film. In addition, under an oxygen pressure of 10-25 atm., the only protective layer on the surface of the alloy comprised of Al2O3. The experimental results demonstrated that the Fe-35Ni-20Cr-4Al-2Nb alloy generated a continuous and dense Al2O3 protective film, and the reduction in oxygen pressure and the addition of Nb elements were favorable for selective external oxidation of Al2O3.

Thermodynamic Assessment of the P2O5-Na2O and P2O5-MgO Systems.

Knowledge about the thermodynamic equilibria of the P2O5-Na2O and P2O5-MgO systems is very important for controlling the phosphorus content of steel materials in the process of steelmaking dephosphorization. The phase equilibrium and thermodynamic data of the P2O5-Na2O and P2O5-MgO systems were critically evaluated and re-assessed by the CALPHAD (CAlculation of PHAse Diagram) approach. The liquid phase was described by the ionic two-sublattice model for the first time with the formulas (Na+1)P(O-2, PO3-1, PO4-3, PO5/2)Q and (Mg+2)P(O-2, PO3-1, PO4-3, PO5/2)Q, respectively, and the selection of the species constituting the liquid phase was based on the structure of the phosphate melts. A new and improved self-consistent set of thermodynamic parameters for the P2O5-Na2O and P2O5-MgO systems was finally obtained, and the calculated phase diagram and thermodynamic properties exhibited excellent agreement with the experimental data. The difference in the phase composition of invariant reactions from the experimentally determined values reported in the literature is less than 0.9 mol.%. The present thermodynamic modeling contributes to constructing a multicomponent oxide thermodynamic database in the process of steelmaking dephosphorization.

Kinetic and Thermodynamic Interplay of Polymer-Mediated Liquid-Liquid Phase Separation for Poorly Water-Soluble Drugs.

Understanding the interplay between kinetics and thermodynamics of polymer-mediated liquid-liquid phase separation is crucial for designing and implementing an amorphous solid dispersion formulation strategy for poorly water-soluble drugs. This work investigates the phase behaviors of a poorly water-soluble model drug, celecoxib (CXB), in a supersaturated aqueous solution with and without polymeric additives (PVP, PVPVA, HPMCAS, and HPMCP). Drug-polymer-water ternary phase diagrams were also constructed to estimate the thermodynamic behaviors of the mixtures at room temperature. The liquid-liquid phase separation onset point for CXB was detected using an inline UV/vis spectrometer equipped with a fiber optic probe. Varying CXB concentrations were achieved using an accurate syringe pump throughout this study. The appearance of the transient nanodroplets was verified by cryo-EM and total internal reflection fluoresence microscopic techniques. The impacts of various factors, such as polymer composition, drug stock solution pumping rates, and the types of drug-polymer interactions, are tested against the onset points of the CXB liquid-liquid phase separation (LLPS). It was found that the types of drug-polymer interactions, i.e., hydrogen bonding and hydrophobic interactions, are vital to the position and shapes of LLPS in the supersaturation drug solution. A relation between the behaviors of LLPS and its location in the CXB-polymer-water ternary phase diagram was drawn from the findings.

Towards the selective growth of two-dimensional ordered CxNy compounds via epitaxial substrate mediation.

Two-dimensional (2D) ordered carbon-nitrogen binary compounds (CxNy) show great potential in many fields owing to their diverse structures and outstanding properties. However, the scalable and selective synthesis of 2D CxNy compounds remain a challenge due to the variable C/N stoichiometry induced coexistence of graphitic, pyridinic, and pyrrolic N species and the competitive growth of graphene. Here, this work systematically explored the mechanism of selective growth of a series of 2D ordered CxNy compounds, namely, the g-C3N4, C2N, C3N, and C5N, on various epitaxial substrates via first-principles calculations. By establishing the thermodynamic phase diagram, it is revealed that the individualized surface interaction and symmetry match between 2D CxNy compounds and substrates together enable the selective epitaxial growth of single crystal 2D CxNy compounds within distinct chemical potential windows of feedstock. The kinetics behaviors of the diffusion and attachment of the decomposed feedstock C/N atoms to the growing CxNy clusters further confirmed the feasibility of the substrate mediated selective growth of 2D CxNy compounds. Moreover, the optimal experimental conditions, including the temperature and partial pressure of feedstock, are suggested for the selective growth of targeted 2D CxNy compound on individual epitaxial substrates by carefully considering the chemical potential of carbon/nitrogen as the functional of experimental parameters based on the standard thermochemical tables. This work provides an insightful understanding on the mechanism of selective epitaxial growth of 2D ordered CxNy compounds for guiding the future experimental design.

Polymer Characteristics for Drug Layering on Particles Using a Novel Melt Granulation Technology, MALCORE®.

MALCORE®, a novel manufacturing technology for drug-containing particles (DCPs), relies on the melt granulation method to produce spherical particles with high drug content. The crucial aspect of particle preparation through MALCORE® involves utilizing polymers that dissolve in the melt component, thereby enhancing viscosity upon heating. However, only aminoalkyl methacrylate copolymer E (AMCE) has been previously utilized. Therefore, this study aims to discover other polymers and comprehend the essential properties these polymers need to possess. The results showed that polyvinylpyrrolidone (PVP) was soluble in the stearic acid (SA) melt component. FTIR examination revealed no interaction between SA and polymer. The phase diagram was used to analyze the state of the SA and polymer mixture during heating. It revealed the mixing ratio and temperature range where the mixture remained in a liquid state. The viscosity of the mixture depended on the quantity and molecular weight of the polymer dissolved in SA. Furthermore, the DCPs prepared using PVP via MALCORE® exhibited similar pharmaceutical properties to those prepared with AMCE. In conclusion, understanding the properties required for polymers in the melt granulation process of MALCORE® allows for the optimization of manufacturing conditions, such as temperature and mixing ratios, for efficient and consistent drug layering.

Free energy of a two-liquid system of charge carriers in strongly coupled electron and phonon fields and common nature of three phases in hole-doped cuprates.

Hole-doped cuprates exhibit partially coexisting pseudogap (PG), charge ordering (CO) and superconductivity; we show that there exists a class of systems in which they have a single nature as it has recently been supposed. Since the charge-ordered phase exhibits large frozen deformation of the lattice, we develop a method for calculating the phase diagram of a system with strong long-range (Fröhlich) electron-phonon interaction. Using a variational approach, we calculate the free energy of a two-liquid system of carriers with cuprate-like dispersion comprising a liquid of autolocalized carriers (large polarons and bipolarons) and Fermi liquid of delocalized carriers. Comparing it with the free energy of pure Fermi liquid and calculating (with standard methods of Bose liquid theory) a temperature of the superfluid transition in the large-bipolaron liquid we identify regions in the phase diagram with the presence of PG (caused by the impact of the (bi)polarons potential on delocalized quasiparticles), CO and superconductivity. They are located in the same places in the diagram as in hole-doped cuprates, and, as in the latter, the shape of the calculated phase diagram is resistant to wide-range changes in the characteristics of the system. As in cuprates, the calculated temperature of the superconducting transition increases with the number of conducting planes in the unit cell, the superfluid density decreases with doping at overdoping, the bipolaron density (and bipolaronic plasmon energy) saturates at optimal doping. Thus, the similarity of the considered system with hole-doped cuprates is not limited to the phase diagram. The results obtained allow us to discuss ways of increasing the temperature of the superfluid transition in the large-bipolaron liquid and open up the possibility of studying the current-carrying state and properties of the bipolaron condensate.

A nonionic microemulsion co-loaded with atorvastatin and quercetin: Simultaneous spectroscopic analysis and payload release kinetics.

In this study, we have co-loadedatorvastatin (ATR) and quercetin (QCT) in a nonionic microemulsion. After developing a derivative ratio spectrophotometric technique for simultaneous analysis of ATR and QCT, pseudoternary phase diagram was constructed utilizing1:4 d-α-tocopherol polyethylene glycol 1000 succinate (TPGS) and ethanol as surfactant and cosurfactant, respectively. Oleic acid was used as oil phase. Structural characterization of the formulation was carried out along a water dilution line created in monophasic region. Characterizations at these dilution points were performed using dynamic light scattering and polarized light microscopy. The average hydrodynamic size of the optimized formulation was found to be 18.9 nm and it did not change upon loading of ATR and QCT. In vitro release was assessed for the formulations loaded with different ratios of ATR and QCT, and the data were fitted to different mathematical models. Interestingly, we noticed differences in release kinetics during changes in dose ratios, particularly for QCT. Higuchi kinetics, observed at equal dose, shifted to Korsmeyer-Peppas model at higher QCT-ATR ratio (2:1 and 4:1). This difference is attributable to the ability of QCT molecules of overwhelming the interface at higher concentrations. Altogether, our observations highlight that the ratio of payloads should be selected carefully in order to avoid unpredictable release patterns.